Polymers of amino epoxides



United States Patent 3,403,114 POLYMERS OF AMINO EPOXIDES Edwin J.Vandenberg, Foulk Woods, Del., assignor to Hercules Incorporated,Wilmington, Del., a corporation of Delaware No Drawing.Continuation-impart of application Ser. No. 369,322, May 21, 1964. Thisapplication Feb. 17, 1967, Ser. No. 616,781

12 Claims. (Cl. 260-2) ABSTRACT OF THE DISCLOSURE Polymers of aminoepoxides, including homopoly-mers, and copolymers with other epoxides,such as alkylene oxides, and the quaternary salts of these amino epoxidepolymers, which polymers are useful as flocculating agents.

This application is a continuation-in-part of my application U.S. Ser.No. 369,322, filed May 21, 1964, which is a continuation-in-part of myapplication U.S. Ser. No. 812,079, filed May 11, 1959, now US.3,135,705, which is in turn a continuation-in-part of my applicationU.S. Ser. No. 738,626, filed May 29, 1958, and now abandoned.

This invention relates to polymers of amino epoxides.

In accordance with this invention, it has been determined that polymershaving certain highly satisfactory properties can be derived byhomopolymerizing an amino epoxide, copolymerizing an amino epoxide withat least one other amino epoxide, or copolymerizing at least one aminoepoxide with other epoxides that do not contain an amino group. Blockcopolymers of an amino epoxide and another epoxide can also be preparedin accordance with this invention.

The polymers of this invention can be derived from amino epoxides havingthe formula R and R" are the same or difierent radicals and are selectedfrom the group consisting of alkyl which can be straight chain orbranched chain alkyl having from 1 through 20 carbon atoms such, forexample, as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl,isobutyl, n-pentyl, nhexyl, n-heptyl, n-octyl, 2,4-dimethyloctyl,dodecyl, and octadecyl,

cycloalkyl such as cyclopentyl, cyclohexyl, and cycloheptyl,

aryl such as phenyl, diphenyl, and naphthyl, haloaryl such aschlorophenyl, bromophenyl, dichlorophenyl, and the like,

alkaryl such as methylphenyl, dimethylphenyl, ethylphenyl, and the like,

aralkyl such as benzyl, and the like,

aryloxyalkyl such as phenoxyrnethyl, phenoxyethyl,

phenoxypropyl, and the like,

alkoxyalkyl such as methoxymethyl, methoxyethyl,

ethoxymethyl, ethoxyethyl, and the like;

A is a bivalent radical selected from the group consisting alkylene suchas methylene, ethylene, trimethylene,

tetramethylene, and the like,

cycloalkylene such as cyclopentylene, cyclohexylene,

and cycloheptylene,

arylene such as phenylene, and the like,

3,403,114 Patented Sept. 24, 1968 and n is an integer of from 1 through3, n is an integer of "from 0 through 1, R is selected from the groupconsisting of (RR"N) (A)(OCH wherein R, R", A, n and n are as abovedefined,

hydrogen, alkyl such, for example, as those above enumerated, aryl such,for example, as those above enumerated, haloaryl such, for example, asthose above enumerated, alkaryl such, for example, as those aboveenumerated, aralkyl such, for example, as those above enumerated,aryloxyalkyl such, for example, as those above enumerated, andalkoxyalkyl such, for example, as those above enumerated.

In the above formula, when A is arylene, such as phenylene, R and R can,in addition to being one of the radicals above enumerated, be hydrogen.Also when A is alkylene then it is one, and when A is cycloalkylene,

arylene,

CH2 CH2 then n can be 1, 2, or 3.

Specific examples of amino epoxides that can be homopolymerized orcopolymerized in accordance with this invention include The aminoepoxides can be homopolymerized, copolymerized to form normal randomcopolymers with other amino epoxides, or copolymerized with otherepoxides containing no amino group. Block copolymers can be prepared byfirst polymerizing one monomer or monomer mixture followed by theaddition to the polymerization reaction mass of a second differentmonomer or monomer mixture. In preparing block copolymers, the monomerscan be added to the polymerization reaction vessel in any order,although it is preferred to add the amino epoxide monomer last.

Also, and in accordance with this invention, it has been determined thatan amino epoxide, as above defined, can be converted by known methods tothe quaternized form thereof and subsequently homopolymerized orcopolymerized with a different monometer which can be an amino epoxide,a quaternized amino epoxide, or an epoxide containing no amino group.

The quaternized amino epoxides have the formula wherein R, R, R", A, n,and n are as above defined, R is an alkyl, cycloalkyl, or aralkyl such,for example,

'as the alkyl, cycloalkyl and aralkyl radicals above enumerated, R canbe the same as R or R" or it can be a different radical, and Xrepresents an anion selected from the group consisting of anions of saltforming acids such as Cl, Br-, 1*, F, 80 and R COO such as stearate,formate, acetate, benzoate, fatty acid anions, and resin acid anions. Rrepresents a hydrocarbon radical such as alkyl, cycloalkyl, aryl,alkaryl, aralkyl, and haloalkyl.

The cyclic amino epoxides can also be homopolymerized or copolymerizedin accordance with this invention. These compounds have the formula(III) oRgY)m n cn \O/ wherein m is an integer of from 3 through 10, R isselected from the group consisting of hydrogen and alkyl such as methyl,ethyl, propyl, and isopropyl, and Y is selected from the groupconsisting of hydrogen and RR"N- wherein R and R" are as above defined,and wherein at least one Y is R'RN. Specific examples of these compoundsinclude 3-dimethylamino-1,2-epoxycyclohexane,4-dimethylamino-1,2-epoxycyclohexane,4-diethylamino-1,2-epoxycyclohexane,4-methylethylamino-1,2-epoxycyclohexane,

3 ,4-bis (diethylamino) -1,2-epoxycyclohexane,

3,5 -bis (diethylamino 1 ,2-epoxycyclohexane,S-dimethylaminophenyl-1,2-epoxycyclohexane,4-diethylamino-1,2-epoxycycloheptane,

3 -diethylamino-1,2-epoxycyclooctane,4-diethylamino-1,2-epoxycyclododecane,3-dimethylamino-1,2-epoxycyclopentane,4-diethylamino-1,2-epoxycyclopentane,4-dimethylamino-S-methyl-1,2-epoxycyclohexane, and4-methylethylamino-5-isopropyl-1,2-epoxycyclohexane.

The quaternized form of these compounds can be employed also.

Other epoxides containing no amino group that can be copolymerized withat least one amino epoxide or quaternized amino epoxide include thealkylene oxides such as ethylene oxide, propylene oxide, butene-l-oxide,cisbutene-2-oxide, trans-butene-Z-oxide, and isobutylene epoxide; thesubstituted alkylene oxides such as epichlorohydrin, epibromohydrin,methallyl chloride epoxide, trifiuoromethyl ethylene oxide,perfiuoropropylene oxide, perfluoroethylene oxide, vinyl chlorideepoxide, dichloroisobutylene epoxide, 1,2 dichloro 3,4 epoxybutane,1-chloro-3,4-epoxybutane, 1 chloro 4,5 epoxypentane, 1,1-dichloro-2,3-epoxypropane, 1, 1, 1-trich1oro-2,3-epoxypropane, and 1,1,1 trichloro3,4 epoxybutane; cycloaliphatic epoxides such as the cyclohexene oxides,the

vinyl cyclohexene oxides (monoand dioxides), a-pinene epoxide, anddipentene epoxide; epoxy ethers such as the alkyl glycidyl ether as, forexample, methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidylether, isobutyl glycidyl ether, tert-butyl glycidyl ether, n-hexylglycidyl ether, n-octyl glycidyl ether, and the like; phenyl glycidylether, the chlorophenyl glycidyl ethers, the nitrophenyl glycidylethers, the alkylphenyl glycidyl ethers, the chloroalkyl glycidylethers, such as chloroethyl glycidyl ether, bromoethyl glycidyl ether,and 2-chloro-1-methyl ethyl glycidyl ether, unsaturated glycidyl etherssuch as vinyl glycidyl ether, allyl glycidyl ether, and o-allylphenylgycidyl ether; glycidyl esters such as glycidyl acetate, glycidylpropionate, glycidyl pivalate, glycidyl methacrylate, glycidyl acrylate,and the like; alkyl glycidates such as methyl glycidate and ethylglycidate; and other epoxides as, for example, styrene oxide,u-methylstyrene oxide, butadiene monoand dioxides, epoxy stearates, andtrimethyl 2,3-epoxypropyl ammonium chloride.

Any organoaluminum compound reacted with water can be used as thecatalyst for the polymerization of amino epoxides in accordance withthis invention. These catalysts are disclosed and described inapplication Ser. No. 812,079, filed May 11, 1959, now U.S. 3,135,705,reference to which is hereby made.

Thus, the polymers of this invention can be prepared by contacting anamino epoxide with a catalyst formed by reacting an organoaluminumcompound containing at least one aluminum-to-carbon bond, such astriethylaluminum, with water in an amount such that the molar ratio ofwater to organoaluminum compound is within the range of from about 0.1to about 1.5 and is lower than the number of aluminum-to-carbon bonds inthe organoaluminum compound.

Any desired procedure can be used for reacting the organoaluminumcompound with the specified molar ratio of water. Preferred methods aredisclosed and described in U.S. 3,135,705.

Also, the organoaluminum compound can be first reacted with from about0.01 mole to about 1.5 moles of a chelating agent, such asacetylacetone, prior to reaction with water to provide a satisfactorycatalyst. Suitable chelating agents are disclosed in U.S. 3,135,705.

Any amount of the organoaluminum-water reaction product can be used tocatalyze the polymerization process in accordance with this inventionfrom a minor catalytic amount up to a large excess but, in general, willbe within the range of from about 0.2 to 10 mole percent based on themonomer being polymerized and preferably will be within the range offrom about 1 to about 5 mole percent based on the monomer beingpolymerized.

The polymerization reaction can be carried out by any desired means,either as a batch or continuous process with the catalyst added all atone time or in increments during the polymerization or continuouslythroughout the polymerization. If desired, the monomer may be addedgradually to the polymerization system.

The polymerization reaction can be carried out as a bulk polymerizationprocess, in some cases at the boiling point of the monomer (reduced to aconvenient level by adjusting the pressure) so as to remove the heat ofreaction. However, for ease of operation, it is more generally carriedout in the presence of an inert diluent. Any diluent that is inert underthe polymerization reaction conditions can be used as,- for example,ethers such as the dialkyl,

aryl, or cycloalkyl ethers as, for example, diethyl ether,

dipropyl ether, diisopropyl ether, aromatic hydrocarbons such asbenzene, toluene, and the like, or saturated aliphatic hydrocarbons andcycloaliphatic hydrocarbons such as n-heptane and cyclohexane, andhalogenated hydrocarbons as, for example, chlorobenzene or haloalkenessuch as methyl chloride, methylene chloride, chloroform, carbontetrachloride and ethylene dichloride. Mixtures of two or more diluentscan be used and in many cases are preferable. For example, whensaturated aliphatic hydrocarbons are used as a diluent, it ispreferable, particularly if high molecular weight polymers are desiredor if very little diluent is present, to use them in admixture withethers. A complexing agent for the organoaluminum compound, such asether, tetrahydrofuran, and the like, can be used and is particularlydesirable in a bulk polymerization process.

The polymerization process in accordance with this invention can becarried out over a wide temperature range and pressure. Usually, it willbe carried out at a temperature from about 80 C. up to about 250 0.,preferably from about 80 C. to about 150 C. and more preferably withinthe range of about -30 C. to about 100 C. Usually, the polymerizationprocess will be carried out at autogeneous pressure, butsuperatmospheric pressures up to several hundred pounds can be used ifdesired, and, in the same way, subatmospheric pressures can also beused.

While the catalysts described above are preferred for use in carryingout this invention, there can be employed as a catalyst for thepolymerization of the amino epoxides a halogen-free organomagnesiumcompound that has been reacted with at least one polyreactive compound.The amount of the total polyreactive compound that is reacted with theorganomagnesium compound is important and should be an equivalent moleratio within the range of from about 0.01 to about 0.7, and preferablyfrom about 0.05 to about 0.5, of the polyreactive compound to theorganomagnesium compound.

Any organomagnesium compound, which contains no halogen, when reactedwith a polyreactive compound can be used as a catalyst for thepolymerization of amino epoxides. Preferably, the organomagnesiumcompound will have the formula RR'Mg where R is any hydrocarbon radical,as for example, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl,cycloalkylaryl, and the like, and R is the same as R or is H, OR, NR SR,and the like. Exemplary of the organornagnesium compounds that can beused for the preparation of the catalyst are dimethylmagnesium,diethylmagnesium, dipropylmagnesium, diisopropylmagnesium,di-n-butylmagnesium, diisobutylmagnesium, di- (tert-butyl)-magnesiurn,diamylmagnesium, dioctylrnagnesium, dicyclohexylmagnesium,diphenylmagnesium, ethylmagnesium hydride, butylmagnesium hydride,methoxy methylmagnesium, and ethoxy ethylmagnesium. Mixtures of any ofthese organornagnesium compounds can be used.

As pointed out above, the organomagnesium compound used as a catalyst inthis invention is reacted with a polyreactive compound. The termpolyreactive compound is intended to mean any compound, organic orinorganic, which has at least two sites for reaction with theorganomagnesiurn compound. Thus, any compound which has at least twogroups or sites to react with organomagnesium compounds to form an O Mg,S-Mg, N-Mg, PMg, CMg, and the like, bond can be used. Such polyreactivecompounds are compounds containing at least two active hydrogens,compounds containing one active hydrogen and one of the group selectedfrom oxygen doubly bonded to carbon (C O), oxygen doubly bonded tonitrogen (N O), oxygen doubly bonded to sulfur (S O), oxygen doublybonded to phosphorus (P O), sulfur doubly bonded to carbon (C S), sulfurdoubly bonded to phosphorus (P S), nitrogen doubly bonded to nitrogen (NN), and nitrogen triply bonded to carbon (GEN), compounds containing noactive hydrogen and at least two groups selected from C O, N O, S O, PO, C S, P S, CEN, and N S, and such polyreactive compounds as carbonmonoxide and nitric oxide. As is well known, an active hydrogen is ahydrogen in a compound, organic or inorganic, wherein the hydrogen isattached to a nonmetallic element other than carbon such as oxygen,sulfur, nitrogen, phosphorus, and the like, and, therefore, active. Itcan also be hydrogen attached to carbon wherein the hydrogen atom is aso-called acidic hydrogen or hydrogen activated by the presence of someactivating group (an electron withdrawing group) in the a-position tothe carbon to which the active hydrogen is attached, as for example,hydrogen bound to a carbon or to a C O group, a to a COOR group, on toan S O group, or to an N O group, a to a CEN group or the equivalent NECgroup, etc. Thus, the active hydrogen can be that present in one of theCHSO and COOH.

Exemplary of the active hydrogen compounds containing at least twoactive hydrogens that can be used as the polyreactive compounds for thereaction with the organomagnesium compound to form the catalyst arewater; alkylene glycols and cycloaliphatic polyols, such as ethyleneglycol, trimethylene glycol, tetramethylene glycol, pentamethyleneglycol, glycerol, pentaerythritol, trimethylol propane,2-butene-1,4-diol, 2-butyne-1,4-diol, 1,3-cyclohexanediol,1,4-cyclohexanediol, and the like; polyhydric phenols such asresorcinol, hydroquinone, pyrocatechol, bisphenol A(p,pisopropylidenediphenol); ammonia; amines such as methylamine,ethylamine, n-butylamine, amylamines, and the like, arylamines, such asaniline, aralkylarnines, such as benzylamine, cycloalkylamines, such ascyclohexylamine, diamines, such as ethylenediamine, diethylene triamine,triethylene tetrarnine, hexamethylene diamine, p-phenylenediamine,piperazine; hydroxylamine; aminoalcohols, such as ethanolamine andtetrahydroxyethyl ethylene diamine; hydrazine; phenyl hydrazine, amidessuch as urea, thiourea, acetamide, malonamide, and the like;sulfenamides and sulfonamides such as p-toluene sulfonamide; hydrogensulfide; dimercaptans, such as ethanedithiol, 1,5-pentanedithiol, anddithioresorcinol; Z-mercaptoethylamine; dialkyl sulfides, dialkyldisulfides, dialkyl polysulfides; sulfones and hydroxysulfones, such asdibutylsulfone, hydroxyethyl methyl sulfone; sulfoxides, such as dibutylsulfoxide, dimethyl sulfoxide; acids such as sulfuric acid, sulfurousacid, phosphorus acid, phosphoric acid, carbonic acid, acetic acid,oxalic acid, phthalic acid, ethylenediamine tetraacetic acid,cc,adiOCtyl ethylenediamine diacetic acid, malonic acid, succinic acid,adipic acid, ketones, such as acetone, diacetyl, dibenzoylmethane, 2hydroxyethyl methyl ketone, acetylacetone, acetonylacetone,diacetylacetone, acetophenone; esters, such as malonic esters, as forexample, methyl malonate and ethyl malonate, acetoacetic acid, esterssuch as ethyl acetoacetate; nitro or nitroso alkanes such asnitromethane, nitroethane, and nitrosomethane; nitriles and isocyanides,such as acetonitrile and hydracrylonitrile 3 hydroxy propionitrile); thehydrate of formaldehyde; (HNS) and the like. Obviously, many otheractive hydrogen compounds wherein there are present in the molecule atleast two active hydrogens can be used.

Exemplary of other polyreactive compounds that can be reacted with anorganomagnesium compound to form the catalysts used in this inventionare compounds containing one active hydrogen and one C O group, as forexample, benzoic acid; compounds containing one active hydrogen and oneN O group, such as nitrosophenol; compounds containing one activehydrogen and one S O group such as benzene sulfinic acid; compoundscontaining one active hydrogen and one P O group, as for example,dimethyl hydrogen phosphite; compounds containing one active hydrogenand one C S group such as dithiobenzoic acid; compounds containing oneactive hydrogen compound and one P S group such as esters ofdithiophosphoric acid; compounds containing one active hydrogen and oneCEN group such as hydrogen cyanide; compounds containing at least two CO groups and no active hydrogen such as carbon dioxide, glyoxal, thedialkyl esters or oxalic acid, and the like; compounds containing atleast two P S groups and no active hydrogen,

as for example, phosphorus pentasulfide; compounds conpounds containingat least two S=O groups and no active hydrogen, such as sulfur dioxide;compounds containing at least two P=O groups and no active hydrogen,such as phosphorous pentoxide and tributyl phosphate; compoundscontaining at least two C=S groups and no active hydrogen such as carbondisulfide; compounds containing at least two P S groups and no activehydrogen, as for example, phosphorus pcntasulfide; compounds containingat least two N=S groups and no active hydrogens, such as nitrogensulfide (N 5 compounds containing at east two CEN or NEC groups and noactive hydrogen, as for example, cyanogen, phthalyl nitriles, phenyleneisocyanide, and the like; compounds containing :at least one N=N group,as for example, azobenzene; compounds containing at least one C=O groupand at least one N=O group such as nitrosobenzaldehyde andnitrosobenzophenone.

The exact nature of this reaction product is not known; however,regardless of what the nature of the reaction is, it is essential thatthe reaction product retain magnesium to carbon bonds in an amount offrom about 0.2 to about 1.8 hydrocarbon group per magnesium atom, andpreferably from about 0.4 to about 1.2.

The amount of the polyreactive compound that is reacted with theorganomagnesium compound will depend on the polyreactive compound, theorganomagnesium compound, and the like, and to some extent upon thediluent, temperature, and the epoxide being polymerized. In any event,it should be within the range of from about 0.01 to about 0.7 mole permole equivalent of magnesium compound, preferably from about 0.05 toabout 0.6 and more preferably from about 0.1 to about 0.4, based on adifunctional reactive compound. Thus, in the case of a difunctionalpolyreactive compound such as water, one would use from about 0.02 toabout 1.4 mole of water per mole of organomagnesium compound andpreferably from about 0.1 to about 1.2 mole of water per mole ofmagnesium. If the polyreactive compound contains more than two reactivesites, the amount of the polyreactive compound will be reducedproportionately. In the case of magnesium compounds having the formulaMgRR Where R is organo and R is other than H or R, the ratio ofpolyreactive compound will be lower, as for example, in the range offrom about 0.01 to about 0.35 mole equivalents. Below or above theseratios the polymerization is retarded or otherwise adversely affected,as for example, there is produced a liquid polymer instead of a highmolecular weight solid polymer. By the term equivalent mole ratio" asused in this specification and claims is meant the moles of polyreactivecompound containing two reactive sites per equivalent of magnesiumcompound.

Any desired procedure can be used for reacting the organomagnesiumcompound with the specified ratio of the polyreactive compound. It ispreferred that the organomagnesium compound and the polyreactivecompound be prereacted by adding the specified amount of thepolyreactive compound to a solution or dispersion of the organomagnesiumcompound in an inert diluent, as for example, a hydrocarbon diluent,such as n-hexane, n-heptane, branched aliphatic hydrocarbons, aromatichydrocarbons, such as benzene and toluene, cycloaliphatic hydrocarbons,such as hexane and methylcyclohexene, or an ether such as diethyl etherand diisopropyl ether, or a mixture of such diluents. The reaction ofthe organomagnesium compound and the active hydrogen compound can alsobe carried out by reacting the two reagents in situ in thepolymerization reaction mixture.

In some cases it has been found to be advantageous to react theorganomagnesium-polyreactive compound reaction product with a complexingagent, as for example, an ether such as diethyl ether, tetrahydrofuran,and dioxane, a thioether, an aminoether, a tertiary amine, or a tertiaryphosphine. In this case the organomagnesium compound can be reactedfirst with the polyreactive compound, and then with the complexingagent, or the latter can be added to the polymerization diluent, or thecomplexing agent can be present while forming the catalyst. The amountof complexing agent reacted with the catalyst varies widely with thenature of the complexing agent. Thus, with weak complexing agents suchas diethyl ether and dioxane, one can use from 0.1 up to 100 or moremoles per magnesium, and with stronger complexing agents such astertiary amines, phosphines, some cyclic ethers, and the like, an amountof from 0.1 mole to about 10 moles per magnesium can be used, andpreferably from about 1 mole to about 3 moles per magnesium is used. Inthe case of the weaker 'complexing agents such as diethyl diluent forthe polymerization.

Any amount of the organomagnesium reaction product prepared as describedabove can be used to catalyze the polymerization process from a minorcatalytic amount up to a large excess, but in general, will be withinthe range of from about 0.2 to 10 mole percent based on the magnesiumand the monomer or monomers being polymerized and preferably will bewithin the range of from about 1 to about 5 mole percent. The amountused depends in part on such factors as monomer purity, diluent purity,and the like, less pure epoxides and diluents requiring more catalyst todestroy reactive impurities.

The following examples are illustrative of this invention. All parts andpercentages are by weight unless otherwise indicated. The molecularweight of the polymers produced in these examples is shown by theReduced Specific Viscosity (RSV). The term Reduced Specific Viscositymeans the e /c determined on a solution of the polymer in a givendiluent. Unless otherwise noted, the RSV of the polymers of thefollowing examples was determined on a 0.1% solution of the polymer inchloroform at 25 C.

EXAMPLE 1 Into a polymerization vessel filled with nitrogen there wereplaced 9.9 parts of ethylene oxide, 0.1 part of 1diethylamino-2,3-epoxypropane, and 31.4 parts of n-heptane. The vesseland its contents were equilibrated at 30 C. There was then added to thevessel a catalyst prepared from 0.23 part of triethylaluminum which hadbeen reacted with 1.0 mole of acetylacetone per mole of aluminum and 0.5mole of water per mole of aluminum in a :30 etherzn-heptane mixture.This catalyst was prepared by reacting a 0.5 M solution oftriethylaluminum in 70:30 etherzn-heptane with 1 mole of acetylacetoneper mole of aluminum at 0 C., agitating the mixture for 22 hours at 30C., adding 0.5 mole of water per mole of aluminum with agitation, andthen reacting the resulting mixture for 20 hours at 30 C. After 1.2hours of polymerization reaction time, another equal portion of thecatalyst was added to the reaction mass. After 7 hours, during whichtime the temperature of the reaction mass was maintained at about 30 C.,the reaction was stopped by adding to the vessel 4 parts of anhydrousethanol. The resulting reaction mass was then mixed with 35 parts ofdiethyl ether and filtered. The precipitated copolymer was then washedwith diethyl ether, washed with parts of a 0.5% solution of hydrogenchloride in an :20 diethyl etherzmethanol mixture, washed neutral withan 80:20 diethyl etherzmethanol mixture, and then washed once with a0.4% solution of Santonox in diethyl ether. Santonox is a proprietarydesignation for 4,4-thiobis(6- tertbutyl-m-cresol). The washed copolymerwas dried for 16 hours at 50 C. in vacuo. The copolymer, a white solid,had an RSV of 17.9.

EXAMPLE 2 Ethylene oxide and l-diethylamino-Z,3-epoxypropane werecopolymerized in accordance with the procedure of Example 1. In thisexample 9.7 parts of ethylene oxide and 0.3 part ofl-diethylamino-2,3-epoxypropane were employed. The copolymer of ethyleneoxide and l-di- 9 ethylamino-Z,3-epoxypropane produced in this examplehad an RSV of 19.9, and was a white solid.

EXAMPLE 3 Example 1 was repeated using 9 parts of ethylene oxide and 1part of 1-diethylamino-2,3-epoxypropane. The copolymer of ethylene oxideand 1-diethylamino-2,3-epoxypropane thus produced had an RSV of 7.9, andwas a white solid.

EXAMPLE 4 Ethylene oxide, 9.5 parts, 1-diethylamino-2,3-epoxypropane,0.5 part, and dry toluene, 36.5 parts, were placed in a reaction vesselfilled with nitrogen. The vessel and its contents were equilibrated at30 C. There was then injected into the vessel 0.46 part oftriethylaluminum which had been reacted with 0.5 mole of water per moleof aluminum and 0.5 mole of acetylacetone per mole of aluminum. Thiscatalyst was prepared by reacting a 0.5 M solution of triethylaluminumin a 70:30 diethyl etherznheptane mixture with 0.5 mole of water permole of aluminum at C. (the water being added slowly over a 15-minuteperiod), stirring the mixture for 1 hour at 0 C., and then adding 0.5mole of acetylacetone per mole of aluminum over a period of 15 minutes.This mixture was then stirred for 15 minutes at 0 C. and then for 20hours at room temperature (about 25 C.). After 22 hours ofpolymerization reaction time, during which time the temperature of thereaction mass was maintained at about 30 0, another equal portion ofcatalyst was added. After 29 hours the temperature of the reaction masswas raised to 50 C. and the polymerization reaction continued for anadditional 43 hours. The reaction was then stopped by adding to thereaction mass 4 parts of anhydrous ethanol. The product of the reactionwas then precipitated by ad-ding 200 parts of diethyl ether to thereaction mass. The diethyl ether-insoluble precipitate was collected,washed once with diethyl ether and once with a 0.2% solution of Santonoxin diethyl ether. The product was then stirred for 24 hours with 100parts of a 3% aqueous solution of hydrogen chloride. The acid-insolubleportion was collected, washed neutral with water, and dried for 16 hoursat 80 C. in vacuo. This fraction was a tough, rubbery, solid copolymerof ethylene oxide and 1-diethylamino-2,3- epoxypropane which was solublein chloroform and which was amorphous by X-ray diffraction analysis.Elemental analysis showed that the copolymer contained 0.47% nitrogen,indicating that the copolymer contained 5.6%1-diethylamino-2,3-epoxypropane as the hydrochloride. The acid-solubleportion was dialyzed until it was neutral, filtered, the water wasevaporated, and the product was dried. This acid-soluble portion was atough, rubbery, solid copolymer of ethylene oxide andl-diethylamino-2,3-epoxypropane which was crystalilne by X-raydiifraction analysis, which had an RSV of 3.4, and which was comprisedof 2.9% 1-diethylamino-2,3-epoxypropane as the hydrochloride.

EXAMPLE 5 Example 4 was repeated using parts ofl-diethylamino-2,3-epoxypropane. No ethylene oxide monomer was used inthe example. There was obtained a homopolymer of1-diethylamino-2,3-epoxypropane which was a tacky, rubbery material.

EXAMPLE 6 Example 4 was repeated except that 8 parts of ethylene oxideand 2 parts of 1-diethylamino-2,3-epoxypropane were employed. Theether-insoluble, acid-insoluble copolymer obtained was a tough, brownrubber and was comprised of 2.5% 1-diethylamino-2,3-epoxypropane as thehydrochloride. The ether-insoluble, acid-soluble copolymer obtained wasa tough, somewhat rubbery solid which had an RSV of 5.9, which wascrystalline by X- ill my diffraction analysis, and which was comprisedof 3.0% 1-diethylamino-2,3-epoxypropane as the hydrochloride. About 0.10part of the acid-soluble copolymer was agitated 1 day with about 9.9parts of water and only a relatively small amount thereof dissolved inthe water. About 0.03 part of concentrated hydrochloric acid was thenadded. The resulting mixture was agitated for 1 day at room temperature,and there was no visible change in appearance of the mixture. Theinsoluble portion of the mixture was recovered by filtration and foundto be 0.028 part of a brown, rubbery solid which was amorphous by X-raydiffraction analysis, had an RSV of 1.9 as determined on a 0.05%solution thereof in chloroform at 25 C., and which contained 2.1% ofl-diethylamino- 2,3-epoxypropane as the hydrochloride.

EXAMPLE 7 Five parts of 1-diethylamino-2,3-epioxypropane was placed in areaction vessel filled with nitrogen. The reaction vessel wasequilibrated at 30 C. Into the reaction vessel was injected 2.8 parts ofa catalyst solution derived by mixing a 0.5 M solution ofdiethylmagnesium in diethyl ether with 0.8 mole of ammonia per mole ofmagnesium at 0 C. in the presence of glass beads and agitating themixture for 20 hours while maintaining the mixture at 30 C. After 22hours of polymerization reaction time, during which time the reactionmass was maintained at about 30 C., an equal amount of the catalyst wasinjected into the reaction vessel. After 29 hours of reaction time, thetemperature of the reaction mass was raised to 50 C. and thepolymerization reaction continued for an additional 43 hours. Thereaction was stopped by adding 2 parts of anhydrous ethanol to thereaction mass. The reaction mass was then treated in accordance with theseparation procedure of Example 4 except that acetone was substitutedfor diethyl ether in the precipitation and washing steps. About 0.3% ofthe monomer was converted to an acetone-insoluble, acidinsoluble solidpolymer which was tan in color, was in the form of a film, and whichcontained 3.5% sulfate ash. About 2.7% of the monomer was converted toan acetone-insoluble, acid-soluble, rubbery, solid polymer which was inthe form of a film. The polymer had an RSV of 0.73 and was an excellentfiocculating agent.

EXAMPLE 8 Example 4 was repeated using 6 parts of propylene oxide and 4parts of 1-diethylamino-2,3-epoxypropane and with the exception thatafter 45 hours the temperature of the reaction mass was raised to C.,and the equal portion of catalyst was added at 76 hours instead of after22 hours, and the polymerization reaction was then continued for anadditional hours. The acid-insoluble, ether-insoluble copolymer was ahard, brown solid that had an RSV of 0.56, was amorphous by X-raydiffraction analysis, and contained 6.4% l-diethylamino-2,3-epoxypropane as the hydrochloride.

EXAMPLE 9 To a polymerization vessel with a nitrogen atmosphere wascharged 13.6 parts of diethyl ether, 6.7 parts of ethylene oxide and 3.3parts of 1-diethylamino-2,3- epoxypropane. After equilibrating at 30 C.,there was then injected 5.6 parts of a catalyst solution comprising a50:50 mixture of diethyl ether and n-heptane and containing 0.79 part oftriisobutylaluminum reacted with 0.5 mole of water per mole of aluminum,the catalyst solution being added in four portions at 30-minuteintervals. After 19 hours at 30 C. the polymerization was stopped byadding to the reaction mass 4 parts of anhydrous ethanol, and themixture was diluted with 35 parts of diethyl ether. The polymer was thenisolated by centrifugation, washed once with ether and then with ethercontaining 0.2% Santonox. The polymer so obtained when dried was a darkbrown, taffy-like solid. It was then extracted with hot toluene, and thetoluene-insoluble polymer was extracted twice with water. Thewater-soluble fraction was recovered by evaporating the water anddrying. This watersoluble fraction amounted to an 8% conversion and wasa brown, viscous liquid having an RSV of 0.07 in 0.1% solution in waterat 25 C. A nitrogen analysis showed that this copolymer of ethyleneoxide and l-diethylamino-2,3-epoxypropane contained 28% of the aminemonomer. The hot toluene-soluble polymer fraction was dried 16 hours at50 C. in vacuo to provide a solid copolymer having an RSV of 0.14, andthis copolymer contained 26.4% 1-diethylamino-2,3-epoxypropane asindicated by nitrogen analysis. The RSV of this copolymer was .09 asmeasured on a 0.1% solution of the copolymer in water at 25 C.

EXAMPLE 10 Into a polymerization reaction vessel there were chargedparts of propylene oxide and 80 parts of toluene. After equilibratingthe vessel and its contents at 30 0., there was added 0.46 part oftriethylaluminum that had been reacted with 0.5 mole of Water per moleof aluminum and 0.5 mole of acetylacetone per mole of aluminum asdescribed in Example 4. After 19 hours of reaction time at 30 C., thetemperature of the reaction mass was increased to 50 C., and after 3hours at this temperature, the propylene oxide had completelypolymerized. There was then added 5 parts of1-diethylamino-2,3-epoxypropane to the reaction mass and thepolymerization reaction carried out for an additional 24 hours at atemperature of 50 C. The reaction was then stopped by adding to thereaction mass parts of anhydrous ethanol. To the resulting mixture therewas added 0.5% of Santonox based on the weight of the polymer, andsolvent was removed by evaporation. The polymer was then dried for 16hours at 80 C. in vacuo to yield 5.5 parts of a rubbery solid. About 3parts of this product was purified by dissolving it in 120 parts ofacetone and then, while stirring, adding 150 parts of a 3% aqueoussolution of hydrogen chloride. The insoluble portion of this mixture wascollected, washed neutral with water, and dried for 16 hours at 80 C. invacuo to provide 2.5 parts of a snappy rubber which, based on nitrogenanalysis, contained 1.1% 1-diethylamino-2,3-epoxypropane as thehydrochloride, and which had an RSV of 10.8.

EXAMPLE 1 l The polymerization reaction of Example 10 was repeatedexcept that ethylene oxide was used in place of propylene oxide. Thepolymer isolation procedure of Example 4 was employed except that theether-insoluble polymer was dried overnight at room temperature in vacuoto give 5.07 parts of a solid polymer which had an RSV of 11.3. Nitrogenanalysis indicated that the polymer contained 3.1% of1-diethylamino-2,3-epoxypropane. A 1% water solution of this polymer wasvery viscous. A flocculation test showed this product to be a betterflocculating agent than a higher RSV commercial poly(ethylene oxide)fiocculating agent.

EXAMPLE 12 In a polymerization reaction vessel filled with nitrogenthere were mixed 8 parts of ethylene oxide, 2 parts of1-diethylamino-2,3-epoxypropane, and 36.5 parts of toluene. Afterequilibrating the contents of the vessel at C. there was added 5.6 partsof a catalyst solution derived by mixing a 0.5 M solution ofdiethylmagnesium in diethyl ether with 0.8 mole of ammonia per mole ofmagnesium at 0 C. in the presence of glass beads and agitating themixture for 20 hours while maintaining the mixture at 30 C. After 1hours of polymerization reaction time, the polymerization reaction wasstopped by adding to the reaction mass 4 parts of anhydrous ethanol. Thepolymer isolation procedure of Example 11 was employed to give 3.15parts of an ether-insoluble solid polymer which was crystalline by X-rayditfraction analysis and which had an RSV of 14.7. Nitrogen analysisindicated that the polymer contained 5.1% of 1-diethylamino-2,3-epoxypropane. This polymer was a good fiocculating agent. A 1% aqueoussolution of the polymer was very viscous. The water solution of thepolymer contained some insoluble polymer which was recovered. Thiswatersoluble polymer was 88% of the total polymer produced, had an RSVof 14.4, and was crystalline by X-ray diffraction analysis. Nitrogenanalysis indicated that the Watersoluble polymer contained 3.7% 1-diethylamino-2,3- epoxypropane. A tough, glossy film was prepared fromthe ether-insoluble polymer by molding it at 150 C. for 2 minutes undera pressure of about two tons per square inch. The film was drawn at roomtemperature to give a tough, oriented film. This polymer can also besolution spun or melt spun into the form of fibers which can besubsequently oriented by known procedures.

EXAMPLE 13 The polymerization reaction of Example 10 was repeated exceptthat 5 parts of a C C l-olefin oxide mixture was employed in place ofpropylene oxide, and 73 parts of toluene was employed instead of 80parts. Also, twice as much catalyst was employed than that employed inExample 10, and the polymerization reaction was carried out for 20 hoursat 30 C. and then for 5 hours at C. before adding the1-diethylamino-2,3- epoxypropane. The reaction mass was diluted withtoluene and then the polymer was precipitated by adding this mixture to4 volumes of methanol containing 1% by weight of Santonox. The insolublepolymer was collected, washed twice with a 1% solution of Santonox inmethanol, and then dried for 16 hours at C. in vacuo to give 4.44 partsof a rubbery, white solid. This polymer had an RSV of 1.4, and nitrogenanalysis indicated that it contained 1.3%1-diethylamino-2,3-epoxypropane.

EXAMPLE 14 Some of the polymers of the above examples were tested foruse as fiocculating agents, and these results are compared withcommercially available poly(ethylene oxide) fiocculating agents. Thetest was run by treating 1000 parts of a 3% slurry of kaolin in water ata pH of 6 with 200 ppm. of the specific polymer (added as a 1% aqueoussolution). The resulting mixture was then stirred for 1 minute, and thenthe settling of the kaolin was observed over a 10-minute period. Thevolume of sedimentation obtained after 2 minutes is a measure of theeffectiveness of the polymer additive as a fiocculating agent. The leastsedimentation volume indicates the most effective fiocculating additive.Table I below sets forth the test results.

TAB LE 1' Additive RSV of Sedimentation Additive Volume, ml.

Polymer of Example 7 0. 73 410 I Good subsidence rate 1 olymor ofExample 12 14. 7 680 somewhat cloudy Polymer of Example 11 i loly(Ethylene Oxide) Commercial Ioly (Ethylene ()xidv) Coagulnnt tlmdu.

supernatant.

EXAMPLES 1519 In each of these examples, a nitrogen filledpolymerization vessel was charged with parts of the monomer, or monomersin the given ratio, and the diluent, 36 parts of toluene in Example 15,and 80 parts of toluene in Examples 16-19. The vessel and contents wereequilibrated at the reaction temperature and there was then added toeach a catalyst prepared from 0.9 part (Example and 0.46 part (Examples16-19) of triethylal uminum that had been reacted with 0.5 mole of waterper mole of aluminum and 0.5 mole of acetylacetone per mole of aluminumas described in Example 4. At the end of the polymerization reactiontime, the reaction was stopped by adding 4 parts of anhydrous ethanol.The homopolymer produced in Example 15 was isolated by adding 5 parts ofacetylacetone and then pouring the mixture into 4 volumes of methanol(the monomer is soluble in methanol), separating the polymer, washing ittwice vw'th methanol and once with a 0.2% solution of Santonox inmethanol and then drying it for 16 hours at room temperature undervacuum. The copolymers produced in Examples 18 and 19 were isolated byadding to the reaction mixture, 0.5% of Santonox (based on a 30%conversion to polymer), and then airdrying the reaction mixture intrays, extracting the films so obtained three times with 3% aqueoushydrogen chloride for2 hours each time, washing neutral and then dryingfor 16 hours at 80 C. under vacuum. The copolymer monomers in the givenratio, and 36 parts of toluene as the diluent. After equilibrating thevessel and contents at the reaction temperature, there was added to each1.0 part of dioctylmagnesium which had been reacted with 0.4 mole ofammonia in Example 20 and 0.5 mole of ammonia in Examples 21-23 .permole of magnesium as described in Example 7 but which catalysts had beenheat-treated at 90 C. for 19 hours. At the end of the polymerizationreaction time, the reaction in Examples 20, 22 and 23 was stopped byadding 4 parts of anhydrous ethanol. The homopolymer produced in Example20 was isolated as described in Example 15. The copolymers produced inExamples 22 and 23 were isolated as described in Examples 17 and 19,respectively. In Example 21, the reaction was stopped by adding 5 partsof a 50:50 ethanolzacetylacetone and 0.5%, based on a 20% conversion topolymer, of the condensation product of croton aldehyde with about 3moles of 3-methyl-6-tert-butylphenol as stabilizer. The polymer wasprecipitated by adding an equal volume of heptane containing 0.3 g. perliter of the above stabilizer. The insoluble polymer was separated,washed twice with the precipitant and dried 16 hours at 50 C. undervacuum.

In Table III are tabulated the monomers and ratio thereof, using thesame abbreviations as used in Table II, the reaction time andtemperature and the percent conversion to isolated polymer, its RSV,percent of the amino epoxide comonomer in the product as determined bynitrogen analysis, and a description of the product.

TABLE III Reaction Conditions Isolated Polymer Example Monomer(s) Temp.,Percent Percent 0. Hours Gonv. RSV Amino Description Comonomer 20 DEAPGE50 19 32 5.9 Methanol insoluble.

ll tulgbery. Low crystalnn y. 21 50 E0, 50 DEAPGE.. 24 42 22. 5 12. 6Heptane insoluble.

Moderate crystallinity. 22 80 E0, 20 DEAPGE 30 19 83 32. 9 5. 7 Etherinsoluble. Highly erysttalline. Orientable p as re. 23 P0, 50 DEAPGE 3019 22 1 2.0 24. 7 Toluene soluble. Snappy rubber.

1 0.1% in benzene at 25 C. of Examples 16 and 17 were isolated by adding4 parts of EXAMPLE 24 acetylacetone to the reaction mixture and thenpouring the mixture into 5 volumes of ether, collecting theetherinsoluble, washing the latter twice with ether and once with 0.2%Santonox in ether and then drying for 16 hours at 50 C. under vacuum.

In Table II are tabulated the monomers and ratio thereof, theabbreviation DEAPGE being used for m-diethylaminophenyl glycidyl ether,E0 for ethylene oxide, and PO for propylene oxide, the reaction time andtemperature and the percent conversion to isolated polymer, its RSV,percent of the amino epoxide comonomer in the product as determined bynitrogen analysis, and a description of the product.

To a nitrogen filled polymerization vessel was charged 9.5 parts ofepichlorohydrin, 0.5 part of diethylaminophenyl glycidyl ether and 36parts of toluene. After equilibrating at 30 C., there was added 5.6parts of a catalyst solution comprising a 50:50 mixture of diethyl etherand n-heptane and containing 0.79 part of triisobutylaluminum reactedwith 0.5 mole of water per mole of aluminum, the catalyst solution beingadded in two portions, the second 19 hours after the first. After 27hours reaction the polymerization was stopped by adding 4 parts ofanhydrous ethanol. The reaction mixture was then diluted with 100 partsof ether, the ether insoluble was separated, washed once with ether,once with a 1% solution of hy- TABLE II Reaction Conditions IsolatedPolymer l I Monomer 5 Tem Percent Percent Examp e C Hours Conv. RSVAmino D%crlption Comonomer 15 DEAP GE 50 16 19 2. 7 Methanol-insolublepolymer. Tacky gum rubber. Low

Eglrlystallirliitbyl. 1 PGE 30 19 3.2 er-inso u e p0 ymer. 16 59 50 DEATough rubber. Moderate E 1pfiystallirliitgyl. 1 20 DEAP GIL.-- 50 1. 65. 1 5. 5 6. 1 er-inso u e p0 yrner. 17 80 E0, Rubbery orientable solid.

Highly crystalline. 18 50 P0, 50 DEAPGE 30 19 6.0 1 2.8 30. 8 Tollgeiesoluble. Snappy rn er 19 80 P0, 20 DEAPGE 50 1. 6 16 X 6. 2 10. 7Tolltetrlie soluble. Tough ru er 1 0.1% in benzene at 25 C.

EXAMPLES 20-23 In each of these examples, a nitrogen filledpolymerizadrogen chloride in ethanol, washed neutral with methanol, thenwashed with a 0.4% solution of Santonox in methation vessel was chargedwith 10 parts of the monomer, or 1101 and dried for 16 hours at 25 C.under vacuum. The

copolymer so obtained amounted to a conversion of 8.5, had an RSV ofabout 1.1 and contained 26% of the amino epoxide as determined bychlorine analysis. It was a tough brown rubber.

EXAMPLE 25 Ten parts of diethylaminophenyl glycidyl ether washomopolymerized following the procedure described in Example 24 butallowing the polymerization to proceed for 163 hours before stopping it,two more portions of the catalyst solution being added at 27 and 43hours. The homopolymer was isolated as described in Example 15. Thepolymer so obtained amounted to a conversion of 21%, had an RSV of 0.6,contained 6.0% nitrogen (theory is 6.3%), and was a tacky rubber.

1 =8 EXAMPLES 28-32 The homopolymer of Example and the copolymers ofExamples 16, 19, 22 and 23 were quaternized by heating a mixture of thepolymer, tetrahydrofuran as diluent, and dimethylsulfate at 50 C. for 24hours. The reaction mixture was diluted with 3 volumes of water,dialyzed until neutral and then was filtered through diatomaceous earth.The quaternized products were isolated by stripping off the diluents at50 C. and then drying for 16 hours at 50 C. under vacuum.

In Table IV are tabulated the polymer used and amount thereof, theamounts of tetrahydrofuran (THF) diluent and of the dimethylsulfate,together with yield based on the sta1ting polymer, percent of aminomonomer present based on nitrogen analysis, the RSV determined on a 0.1%EXAMPLE 26 solution in l M aqueous potassium chloride at C., and Example12 was repeated except that after isolating description of the product.

TABLE IV Isolated Product Parts Parts Example Polymer of Example Parts'IHF Dimethyl Percent; Percent Sulfate Yield Ammo RSV DescriptionMonomer DEAPGE, Homopolymer of 20.... 1. 0 55 10 100 82 3.2 Hard solidfilm. EO-DEAP GE, Copolymer oi16... 0.1 22 5.3 90 16 1.2 Tough film.Moderately crystalline. 30. EO-DEAPGTE, copolymer of 22... 2.0 110 27 0027 1. 7 Tough film. Highly crystalline. 31. IO-DEAPGE, Copolymer area...1.0 22 5.3 50 40 Tacky rubber. 32 PO-DEAPGE, copolymer of 19... 1.0 5514 84 14 2.5 Rubber.

I11sol.

i 0.1% in benzene at 25 C. the 1-diethylamino-2,3-epoxypropanehomopolymer by The quaternized homopolymer produced in Exampleprecipitation with 5 volumes of ether, the ether insoluble 28 was testedfor its flocculation behavior on a 5% was collected, washed twice withether and once with aqueous slurry of a finely divided crystallinesilica hav- 0.2% Santonox in ether and dried. It was then dissolved ingan average particle size of 5 microns and was found in water, thewater-insoluble was removed and the water- 35 to be very effective,250-750 p.p.m., based on the silica, soluble polymer recovered. Itamounted to a conversion effecting rap-id flocculation of the silica. of29%, had an RSV of 14.4, was highly crystalline, was The quaternizedethylene oxide-diethylaminophenyl a soft, orientable film, and contained3.7% of the amino glycidyl ether copolymer produced in Example 29,tested epoxide as determined by nitrogen analysis. This coas describedabove for the homopolymer of Example 28, polymer was tested as aflocculating agent and found to was found to be a good flocculatingagent, 500750 be much better than an even higher molecular weightp.p.m., based on the silica, effecting rapid flocculation ofpolyethylene oxide. the silica.

The polymers of this invention will be comprised of, EXAMPLE 27 byweight, at least about 0.2%, and preferably at least Ten parts of1diethylamino-2,3-epoxypropane was 5 about 2%, of an amino epoxide or aquaternized amino placed in a nitrogen filled reaction vessel andequilibrated epoxide. at 30 C. There was then added 2.0 parts ofdioctyl- The polymers of this invention have utility as floccumagnesiumwhich had been reacted with 0.4 mole of amlating agents; as retentionaids for adding sizing agents, monia per mole of magnesium in a 0.5 Msolution in fillers, and the like to paper; as textile sizes; as dyeingdiethylether at 0 C. in the presence of glass beads, aids for fibers; ascoatings for paper; as protective colagitating for 20 hours at 30 C. andthen heat treating loids; and as cross-linking agents for chlorinatedpolymers for 19 hours at 90 C. After 19 hours, there was added such aspolyepichlorohydrin and poly(vinyl chloride). an equal amount of thecatalyst. After 310 hours at 30 C.. copolymers containing both aminogroups and halogen there Was added, Without isolating the p y 70radicals can be cross-linked at elevated temperatures or Parts ofdiethyl fithel' and 20 Parts of dimethylshltoXide, on prolonged standingwithout requiring vulcanizing followed y 29 Parts Of dimethylsllltatflThe reaction f agents which are often toxic, extractable materials.These allowed to Proceed for 72 hours at The reactloh copolymers thatcan be cross-linked by heating at elevated mixture was Stirred With 250Parts of Water and th@ Water temperatures are useful as potting resinsor encapsulants layer Was then dialyzed until heutfalfor electricalcomponents and the like.

A Portion of the Product was pp of dlhlehts at The block copolymers,especially those derived from and then dried 16 hours at roomtempefature the amino epoxides and long-chain hydrophobic epoxides undervacuum. The quaternized homopolymer of l-dlethylas f example, the o 1 1fi oxides; hydroabietyl J- P YP P 50 Obtained was rubbery ih glycidylether, and the like, are especially useful as paper nature, amounted to12% conversion based on the monosizing agents and as Waterproofingagents f textiles and Contained 89% 0f the Starting mohomer based Theamino epoxide homopolymers and copolymers of on gas chfomotogl'aphy fordiethylmethylamlhe atter'de this invention can also be cross-linked withaliphatic Composition of quaternary hydfoxidh- The qharthrhlzeddihalides such as ethylene dichloride or by blending the P y had an RSVof as measured on a 01% 50111 polymers with a halogen containing polymersuch as :1 tion in 0.1 M aqueous potassium chloride at 25 C.polyepihalohydrin' Another Portion of the Product was tested for itsShaped articles such as molded members, films (oriented fluocculationbehavior on a 5% aqueous slurry of a finely divided crystalline silicahaving an average particle size of 5 microns and was found to be veryeffective, 250-500 p.p.m., based on silica, effecting rapid flocculationof the silica.

and unoriented), and fibers can be prepared from the polymers of thisinvention. Elastomeric fibers can be prepared from these polymers also.

The polymers can be used as the free amine, as a hydrogen halide, as anacid sulfate, as an acid phosphate salt, as a fatty acid, or as a resinacid salt. The amine group can, in some cases, particularly for aminoaryl groups, be converted to a quaternary group by reaction with analkyl halide such as methyl chloride, ethyl chloride, propyl bromide,ethyl fluoride, and the like, or an alkyl sulfate such as ethyl sulfate,methyl sulfate, and the like.

Crystalline and amorphous polymers that will range from hard, rigidsolid materials to solid, rubbery or rubber-like materials are producedin accordance with this invention.

The polymers of this invention will have an RSV of at least about 0.15as determined on a 0.1% solution thereof in chloroform at 25 C.Preferred polymers will have an RSV of about 0.5 and higher, andpreferably greater than about 1.0. The RSV of the polymers can bedetermined in other solvents if required, and the equivalent RSV inchloroform can be calculated therefrom. In the case of water-solublepolymers, the preferred polymers will have an RSV of greater than about0.5 as determined on a 0.1% solution thereof in water and preferablygreater than 1.0. The preferred polymers will have a weight averagemolecular weight of 50,000 and greater and preferably 100,000 andgreater.

By the term epoxide as used in this specification and claims is meantthe oxirane ring, i.e., vicinal epoxides.

It is to be understood that the above description and examples areillustrative of this invention and not in limitation thereof.

What I claim and desire to protect by Letters Patent is:

1. As a new composition of matter, a solid polymer selected from thegroup consisting of homopolymers and copolymers with at least one othervicinal epoxide, said polymer having an RSV of at least about 0.15 asdetermined on a 0.1% solution of the polymer in chloroform at 25% C.derived from an amino epoxide selected from the group consisting of:

(I) an amino epoxide having the formula wherein R and R" each areselected from the group consisting of alkyl, cycloalkyl, aryl, haloaryl,alkaryl, aralkyl, aryloxyalkyl, and alkoxyalkyl, A is a bivalent radicalselected from the group consisting of alkylene, cycloalkylene, arylene,

and

n is an integer of from 1 through 3, n is an integer of from through 1,R is selected from the group consisting of (R'R"N) (A)-(0CH wherein R,

R", A, n, and n are as above defined, hydrogen, alkyl, aryl, haloaryl,aralkyl, aryloxyalkyl, and alkoxyalkyl; and wherein when A is arylene, Rand R" are each selected from the group consisting of hydrogen, alkyl,cycloalkyl, aryl, haloaryl, alkaryl, aralkyl, aryloxyalkyl, andalkoxyalkyl; and wherein when A is alkylene, n is l, and when A isselected from the group consisting of cycloalkylene, arylene,

and

n is an integer of 1 through 3; (II) a quaternized amino epoxide havingthe formula wherein R, R, R", A, n, and n are as above defined, R isselected from the group consisting of alkyl, cycloalkyl, and aralkyl,and

X represents an anion selected from the group consisting of chloride,bromide, iodide, fluoride, sulfate, phosphate, and R COO where R is ahydrocarbon radical; and

(III) an amino epoxide having the formula R )m HOME O wherein m is aninteger of from 3 through 10,

R is selected from the group consisting of hydrogen and alkyl, and

Y is selected from the group consisting of hydrogen and R'R"Nwherein Rand R" are as above defined and wherein at least one Y is R'R"N-.

2. The composition of claim 1 wherein the amino epoxide is1-diethy1amino-2,3-epoxypropane.

3. The composition of claim 2 wherein the polymer is a homopolymer.

4. The composition of claim 2 wherein the polymer is a copolymer of saidamino epoxide and an alkylene oxide.

5. The composition of claim 4 wherein the alkylene oxide is ethyleneoxide.

6. The composition of claim 1 wherein the amino epoxide isrn-diethylaminophenyl glycidyl ether.

7. The composition of claim 6 wherein the polymer is a homopolymer.

8. Th composition of claim 6 wherein the polymer is a copolymer of saidamino epoxide and an alkylene oxide.

9. The composition of claim 8 wherein the alkylene oxide is ethyleneoxide.

10. The composition of claim 3 wherein at least one amino group has beenquaternized.

11. The composition of claim 7 wherein at least one amino group has beenquaternized.

12. The composition of claim 8 wherein at least one amino group has beenquaternized.

References Cited UNITED STATES PATENTS 1,790,042 l/ 1931 Eisleb 260-22,870,100 1/1959 Stewart of a1. 260-2 FOREIGN PATENTS 477,843 1/ 1938Great Britain.

WILLIAM H. SHORT, Primary Examiner.

L. PERTELLA, Assistant Examiner.

U.S. DEPARTMENT OF COMMERCE PATENT OFFICE Washington, DC. 20231 UNITEDSTATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,403,114September 24, 1968 Edwin J. Vandenberg It is certified that errorappears in the above identified patent and that said Letters Patent arehereby corrected as shown below:

Column 6, line 75, "P=S" should read N=O Column 7, line 1, "phosphoruspentasulfide" should read nitrobenzene and nitrogen dioxide Column 8,line 13, after "diethyl" insert ether, the complexing agent may be usedas the sole Signed and sealed this 10th day of February 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

